Aluminum sulfamate antiperspirant preparation



Patented Feb. 19, 1952 ALUIHIN UM SULFAMATE ANTIPERSPIRANT PREPARATION Lester Donald Apperson, Convent Station, and

Earl Leroy Richardson, Fair Lawn, N. J., assignors to Colgate-Palmolive-Peet Company, Jersey City, N. J a corporation of Delaware No Drawing. Original application December 11,

1948, Serial No. 64,905. Divided and this application October 26, 1950, Serial No. 192,378

7 Claims. 1

This invention relates to cosmetic astringent compositions and more particularly to improvements in anti-perspirant preparations.

Among the many anti-perspirants described as having the property of retarding or inhibiting the flow of perspiration the most efiective have been found heretofore to be those containing aluminum salts of strong inorganic acids, e. g. hydrochloric, sulfuric, etc. Cosmetic preparations containing salts of these strong acids, however, have the very serious disadvantage of corroding or tendering clothing fabric, e. g. portions of garments which come in contact with areas of the body on which the preparation is applied. This corrosive action is especially noticeable on fabrics containing cellulosicmaterials such as cotton, rayon and the like. The corrosive effect that is detrimental to fabrics manifests itself particularly where the clothing portion carrying some of the anti-perspirant material is ironed or otherwise subjected to a relatively high temperature before removal of the anti-perspirant preparation. Even long continued contact at ordinary temperatures of cosmetic preparations contain ing aluminum salts of these mineral acids cause weakening or deterioration of the clothing fabric. Of the many salts which have been used or described as useful anti-prespirants, aluminum chloride and aluminium sulfate are by far the most commonly used and have heretofore been considered to be the most effective. However, .both salts show high corrosive action on cotton fabrics, This corrosive action is so severe that considerable research and investigation has been directed to a satisfactory reduction of the corrosive action without simultaneously reducing the anti-perspirant effectiveness of the salts. Because- ,of its less-corrosive action, aluminum sulfate is generally preferred over aluminum chloride.

It has been discovered that the aluminum salt of sulfamic acid is a very efiicacious perspiration retardant, having been found by tests to be definitely superior to the aluminum salt of sulfuric acid in this respect; and, of more importance, it has been observed'that aluminum sulfamate is practically nontendering to clothing fabrics. Under certain severe conditions, however, aluminum sulfamate may cause some discoloration of cellulosic fibers. The discoloration appears as a yellowish to light brown cast when an aluminumsulfamate-containing preparation is japplied to and dried by heat on white fabrics made of cotton, linen or regenerated cellulosic fibers. Therefore, in order to use aluminum sulfa'mate in cosmetic preparations, it became nec- 2 essary to eliminate or reduce to a satisfactor degree its property of causing discoloration of fabrics.

Extensive research was carried out with the object of finding a way to overcome this undesirable discoloration elfect without impairing the efficiency of the aluminum sulfamate as an anti-perspirant. It was discovered that the discoloration tendency could be prevented or satisfactorily lessened by incorporating in the antiperspirant preparation certain organic compounds in sufficient concentration. Compounds found to aid in preventing this discoloration are as follows: Compounds which contain the functional groupECS-H and are soluble in aqueous aluminum sulfamate and which do not precipitate therefrom 'a compound containing aluminum; for example: sodium mercaptopropanesulfonate (1,2), sodium Z-mercaptoethane-l sulfonate, ammonium 2-mercaptoethane 1 sulfonate, ammonium thioglycolate, thioglycolic acid, thiourea and ethylene thiourea.

The extent of solubility of the substance used .as a discoloration inhibitor in the aqueous sulfamate solution may vary with the various compounds and it is essential only that a sufficient quantity of the substance used go into solution to suitably inhibit the discoloration. In some cases the substances may be present in the composition in amounts greater than the limit of solubility without disadvantage. Further, the inhibiting substance used should not reduce the anti-perspirant property of the aluminum sulfamate, nor should it cause the finished prepara- -tion to have an objectionable odor, color or other undesirable characteristics such as cause irritation.

It is, of course, recognized that a few of the compounds listed above and many others which are inoperative in the present invention have been proposed for use in anti-perspirant preparations containing aluminum chloride or aluminum sulfate to prevent serious weakening or the destruotion of fabric due to the corrosive action of these salts. In such preparations, however, the problem was soley to prevent tendering of the fabric since aluminum chloride and sulfate cause no discoloration and there was no reason to suggest that any known anti-tendering agentwould be useful in preparations employing aluminum sulfamate for the entirely different function of preventing discoloration, particularly since tests had demonstrated that no anti-tendering agent was necessary in aluminum sulfamate preparations, nor was there anything to guide the search for anti-discoloring agents.

Test data have further indicated that aluminum sulfamate, either with or without the addition of a discoloration inhibitor from the above described groups produces definitely superior results in inhibiting perspiration when compared with like preparations which contain aluminum sulfate.

To secure such data, specific areas of skin of a number of human subjects were treated daily over a definite period and the perspiration inhibiting eifects for aluminum sulfate and aluminum sulfamate were evaluated. The perspiration from two equal, comparable areas of skin with and without anti-perspirant treatment was periodically collected and weighed. For each measurement a percent of perspiration-lessening effect was calculated as follows: Where X: weight of perspiration on untreated area and Y weight of perspiration on like area treated with anti-perspirant material, then, the perspiration-lessening effect, as represented by (Z), expressed in percent, is as follows:

num sulfamate as the astringent may be used without the addition of corrosion-inhibiting agents. Furthermore, where the cosmetic or other preparation does not come in contact with cotton, muslin, rayon or the like substance whose chief ingredient is cellulose, the discoloration inhibitor may be omitted. For example, wool fibers do not give any discoloration when treated with solutions containing aluminum sulfamate. Where, however, the aluminum sulfamate-containing preparation is to be used for general purposes during which some discoloration may occur which would be objectionable, it is necessary to incorporate a suitable amount of an inhibitor such as described hereinbefore.

The proportion of inhibitor required to prevent discoloration varies with the particular inhibitor. In general, it has been found that it is sufiicient to employ about mol of the effective organic mercapto inhibitor for each mol of aluminum sul-famate in solution. Greater or less quantities of the discoloration inhibitor, or mixtures of different inhibitor compounds may of course be used so long as enough is incorporated to prevent discoloration where the same is objectionable.

In accordance with the present invention, novel anti-perspirant compositions containing aluminum sulfamate may be prepared and marketed in any desired form, e. g., as emulsions, suspensions, solutions, salves, creams, lotions and the like. Such preparations may comprise the usual ingredients including pigments, fillers, perfumes, etc, and they may be compounded in any suitable manner.

The proportion of aluminum sulfamate antiperspirant ingredient to the total composition may be rather widely varied and depends to some extent upon the particular type of preparation, frequency of use, and other variable factors. In general, acomposition should contain sufficient aluminum sulfamate to be effective when cream bases of widely varying composition either with or without a discoloration inhibitor. Generally speaking, such a cream includes an oily phase held in dispersion in an aqueous phase containing the anti-perspirant by one or more suitable emulsifying agents. The oily phase may include such materials as natural and synthetic oils, fats and waxes, e. g. spermaceti, palmityl palmitate, polymerized ethylene oxide (Carbowax), paraffin, sterols, mineral oils, vegetable oils and other esters of fatty acids, etc. Glycerine, propylene glycol, sorbitol and the like emollients may also be present.

Any suitable emulsifying agent may be employed which is sufiiciently stable in acid media.

Examples of emulsifying agents which have been found useful in preparing creams are: partial esters of fatty acids with glycerine, glycol or other polyhydric alcohol, preferably in combination with a stabilizer such as sodium monosulfate monoglyceride of coconut oil fatty acids, diethyloleylamid phosphate, sodium lauryl sulfate, sodium alkyl aromatic sulfonate, etc.

As specific examples of preparations embodying the principles of this invention the following are given without intending to be limited thereby. The parts indicated are by weight.

Example I Parts Glyceryl monostearate 13.00 Spermaceti wax 3.00 Stearyl alcohol 2.00 Mineral oil 1.00

Igepon T (sodium p-oleylethane-amidsulfonate) 2.50 Titanium dioxide 0.50 Aluminum sulfamate 13.00 Ammonium 2-mercaptoethane-1-sulfonate 1.64 Water 63.36

Example II Parts Glyceryl monostearate 15.00 Spermaceti wax 3.00 Mineral oil 2.00 Glycerine 2.00 Titanium dioxide 0.40 Sodium salt of sulfated m-onoglyceride of coconut oil fatty acids 3.00 Aluminum sulfamate 18.00 Sodium mercaptopropanesulfonate (12)., 2.54 Water 54.06

Example III Parts Acid stabilized glyceryl monostearate 13.00 Spermaceti wax 3.00 .Stearyl alcohol 2.00 Igepon T (sodium ,B-oleylethane-amidsulfonate) 3.00 Glycerine 2.50 Aluminum sulfamate 22.50 Ammonium thioglycolate 2.34 Water 51.66

1 Acid stabilized glyceryl monostearate" comprises glyceryl monostearate and a small amount (2 to o% by wt.-) of dietliyloleylamid phosphate.

5, Example IV f Parts Acid stabilized glyceryl monostearate 10.00 Glyceryl monostearate 4.00 Spermaceti wax 4.00 Mineral oil 2.00 Igepon T (sodium fi-oleylethane-amidsulfonate) 2.50; Titanium dioxide 0.50 Aluminum sulfamate 18.00 :Thioglycolic acid 1.59 Water 57.41

" Example V Parts Glycerylmonostearate 13.0 Spermaceti wax' 4:.0 Glycerine -1.0

Sodium salt of sulfated monoglyceride of coconut oil fatty acids 2.3 Titanium dioxide 0.3 Aluminum sulfamate 20.0 Ethylene thiourea 1.6 Water 57.8

Example VI I Parts Diethylene glycol monostearate 16.0

Palmityl palmitate 3.0

Glycerine 1.0 Sodium salt of sulfated monoglyceride of g coconut oil fatty acids 2.5 Titanium dioxide 10.5 Aluminum sulfamate 18.0 Thiourea 6.5 Water 52.5

The aluminum sulfamate cream preparations of Examples I through VI were tested to determine the efiectiveness of the various inhibitors in lessening the discoloration tendency on ifabties. In carrying out the tests the cream was smeared over a cotton swatch (2" x 4" strip) until all of the fabric was covered evenly with no excess cream on the surface. On thereverse side of the strip three drops of water were added to moisten the cloth, and thereafter the strip was placed in an oven and baked at about 214 F. for thirty minutes. These swatches were tested alongside a cotton swatch smeared with a like aluminum sulfamate cream preparation which contained no discoloration Even under the severe conditions of this test, the strip treated with the uninhibited cream was discolored to a greater extent than any of the strips treated with creams of Examples I to VI, and in the case of Examples I, II, IV andVI, there was practically no discoloration. Further, it has been ascertained from tests of the cream containing the inhibitor giving the least eiiect under the severe conditions of the above test that even this substance was efiective in inhibiting this undesirable coloring efiect on fabric when tested under conditions comparable to those'encountered during the normal use of the antiperspirant.

Examples of suitable aluminum sulfamate anti-perspirant solutions which may be used in liquid form or as the water phase in a cream or emulsion-type preparation, such as described in Examples I to VI, are as follows, the parts being by weight:

Example A Parts Aluminum sulfamate 24.9 Sodium 2-mercaptoethane-1-sulfonate 3.1 Water -1 72.0

inhibitor.

a the swatches dipped in Example B Parts Aluminum sulfamate 25.0 Sodium mercaptopropanesulfonate (1,2) 3.4 Water 71.6

Example (I Parts Aluminum sulfamate 24.9 Thiourea 6.0 Water 69.1

The effectiveness of the various discoloration inhibitors in Examples A, B and C were tested'by dipping a cotton swatch into each solution and heating in an oven at about 214 F. for thirty minutes. In each case the discoloration of a similarly treated swatch which had been dipped into a solution of aluminum sulfamate containing no inhibitor was much greater than any of the solutions 01 Examples A,'B, and C.

Aqueous solutions of aluminum sulfamate suitable for main compounding'the anti-perspirant compositions of the invention may be prepared by any appropriate method, such as by reaction of a theoretical amount of sulfamic acid with aluminum hydroxide gel to give a clear solution of aluminum sulfamate. Another method which may be used comprises the reaction of barium sulfamate in an aqueous medium with a theoretical amount of aluminum sulfate to form insoluble barium sulfate which may be removed to leave a clear solution of aluminum sulfamate.

Although the invention has been described in detail and exemplified by numerous examples, it will be understood that the principles of the invention may be made use of by utilizing aluminum sulfamate with modified formulae such as will occur to those skilled in the art.

The present application is a division of patent application Serial Number 64,905, filed December 11, 1948.

Having described the invention what is desired to be secured by Letters Patent is: a

1. A perspirant inhibiting or retarding preparation comprising an aluminum salt of sulfamic acid, in an effective amount from about 5 to about 50% by weight, said aluminum salt having a tendency to discolor cellulosic fibers, and in an amount sufiicient to inhibit said discolouration a compound which contains the functional group ECSH, said compound being soluble in aqueous aluminum sulfamate and not precipitating therefrom a compound containing aluminum.

2. A perspirant inhibiting or retarding preparation in the form of a cream comprising fatty material emulsified with a water-containing phase, an efiective amount of aluminum sulfamate from about 5 to about 50% by weight, said aluminum sulfamate having a tendency to discolor cellulosic fibers, and in an amount suflicient to inhibit said discoloration a compound having the functional group EC-SH which is soluble in aqueous aluminum sulfamate and does not precipitate a compound containing aluminum.

3. A perspirant inhibiting or retarding preparation comprising a water-containing vehicle, aluminum sulfamate in an effective amount from about 5 to about 50% by weight, said aluminum sulfamate having a tendency to discolor cellulosic fibers, and sodium 2-mercaptoethane-1- sulfonate in an amount sufficient to inhibit said discoloration.

4. A perspirant inhibiting or retarding preparation comprising a water-containing vehicle,

7 aluminum sulfamate in an effective amount from about to about 50% by weight, said aluminum sulfamate having .a tendency to discolor cellulosic fibers, and ammonium 2-mercaptoethanel-sulfonate in an amount suihcient to inhibit said discoloration.

5. A perspirant inhibiting or retarding preparation comprising a water-containing vehicle, aluminum sulfamate in an effective amount from about 5 to about 50% by weight, said aluminum sulfamate having a tendency to discolor cellulosic fibers, and ammonium thioglycolate in an amount suflicient to inhibit said discoloration.

6. A cosmetic preparation for inhibiting or retarding perspiration comprising an emulsion of an oleaginous phase and an aqueous phase, and

"including therein aluminum sulfamate in an ef-:-

fective amount from about 5 to about 50% by Weight to inhibit perspiration upon application of said preparation to human skin.

'7. A cosmetic preparation in the form of a cream emulsion for inhibiting or retarding perspiration comprising a cream emulsion of an oleaginous phase held in dispersion in an aqueous phase, an acid stable emulsifying agent therefor to 'maintainsaid emulsion, and as an essential anti-perspirant ingredient aluminum sulfamate in an eifective amount from about 5 to about by weight in solution in said aqueous phase.

LESTER DONALD APPERSON EARL LEROY RICHARDSON.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS OTHER REFERENCES Oberhauser: Chemical Abstracts, vol. 41, April 10, 1947, page 1944. i 

6. A COSMETIC PREPARATION FOR INHIBITING OR RETARADING PERSPIRATION COMPRISING AN EMULSION OF AN OLEAGINOUS PHASE AND AN AQUEOUS PHASE, AND INCLUDING THEREIN ALUMINUM SULFAMATE IN AN EFFECTIVE AMOUNT FROM ABOUT 5 TO ABOUT 50% BY WEIGHT TO INHIBIT PERSPIRATION UPON APPLICATION OF SAID PREPARATION TO HUMAN SKIN. 